Hydrocarbon treating process



United States Patent f Ice Patented June 21, 1960,

This invention relates to the treatment of hydrocarbon oils and is more particularly concerned with the treatment of such oils with a boron chloride treating agent which consists of boron chloride.

The purification of hydrocarbon oil stocks by removal of undesired constituents is an ever-present problem in the petroleum refining industry and many purification processes have been proposed. The removal of various constituents from hydrocarbon oils not only increases the value of the oils but makes them more useful and in some cases easier to handle.

For example, low sulfur crude oils always command a better price than high sulfur crudes. Further, it is easier and more economical to process lower sulfur crude oil because less alloy protection is required. The overall properties of the resulting products such as the color, octane number and lead susceptibility of the gasoline, are generally higher. Since current trends in the petroleum industry point to the increasing use of high sulfur crude oils, the direct desulfurization of crude oil is becoming more and more important. Hughes et al. (Ind. & Eng. Chem. 42, 1879, 1950), suggested the use of hydrogenation for desulfurization only after concluding that less expensive methods were unsatisfactory. Hale et al. (Ind. & Eng. Chem. 41, 2702, 1949), suggested bauxite treatment at 750 F. This method is expensive and not generally applicable to heavy crudes (Burk, US. Patents 2,343,841 and 2,343,744). Hughes et al. (Ind. & Eng. Chem. 43, 750, 1951) used a mixture of boron fluoride and hydrogen fluoride as a sulfur extractive agent. The sulfur removal is satisfactory but the yield is low. In adidtion this extractive agent is highly corrosive and requires pressure in handling.

In the case of lighter distillates such as gasoline, the removal of sulfur increases both the octane number and the lead susceptibility. Numerous methods have been proposed for the removal of mercaptans but few methods have been concerned with the removal of cyclic sulfur compounds. Axe (US. Patent 2,416,465) suggested the use of boron fluoride hydrate as an extractive agent for sulfur removal from light products. Unfortunately, the recovery of the agent is difficult.

The asphaltic constituents in crude oil or other hydrocarbon stocks are undersirable except for use in the manufacture of commercial asphalts. If the crude oil is to be used for the production of light products and as a cracking plant charging stock, especially in a catalytic cracking plant, the asphaltic substances and carbon-like substances are first removed by one of the following four known processes: (1) Coking, which is objectionable because of high investment and troublesome handling of the coke produced, sometimes necessitating mechanical or hydraulic decoking; (2) vacuum distillation, which has serious limitations owing to the fact that when a high vacuum is. used the process becomes uneconomical, whereas if a relatively low vacuum is used the yield of catalytic cracker charging stock is too low and entrainment is also a problem; (3) propane deasphalting ordecarbonizing,

which requires a solvent oil ratio of at least 3 to 1 and also involves pressure operation; and (4) sulfuric acid treatment, which has now become practically obsolete because of operating disadvantages. In the manufacture of lubricating stocks from suitable crude oils, deasphalting and decarbonizing are also necessary steps.

The presence of nitrogen compounds is objectionable in all petroleum and petroleum-like products, especially in catalytic cracker charging stock, because the nitrogen compounds are very effective catalyst poisons. One of the main difliculties in the economical process of shale oil is its high nitrogen content. No commercially feasible method has been heretofore proposed for the removal of nitrogen except by pressure hydrogenation.

'Oxygenated compounds are also objectionable since they lower the heating value of the oil and promote the formation of acids or peroxides, which are corrosive.

Unsaturated compounds occur in various petroleum products. The unstable unsaturated compounds such as: diolefins and acetylenes, which occur only in minor amounts in cracked gasoline, are undesirable, while the mono-olefins in cracked gasoline, and/or Fischer-Tropsch synthetic gasoline are highly desirable as motor fuel.

Color bodies of various types are found in hydrocarbon bodies and are generally considered objectionable. Metallic constituents such as nickel, vanadium and iron are also considered undesirable.

gen treatment and add substantially to the total cost of processing. The quantity of metallic contaminants is not great but these prior pretreatment methods are inherently complex and expensive as well as being time consuming and require large quantities of reagents. There is, therefore, an important need for a means of pretreatment of catalytic reformer charge stock which is effective to reduce the metallic content of the stock to a value which does have an adverse poisoning action upon the oil.

It is an object of this invention to provide an improved process for the removal from hydrocarbon oil stocks of deleterious and/or undesirable constituents such as asphaltic compounds, or more specifically, colloidal car-.

bons, carboids, carbenes, asphaltenes, resins and the like. Another object of the invention is to provide a process for improving the qualities of hydrocarbon oil stocks by the removal of sulfur compounds, especially those of cyclic nature and/ or of high molecular weight.

A further object of this invention is to provide a process for improving the quality of hydrocarbon stocksby the removal of nitrogen compounds.

An additional object of this invention is to provide a process for removing oxygen compounds from hydrocarbon oil stocks.

A still further object of the invention is the provision of a process for removing unstable unsaturated compounds from hydrocarbon oil stocks without adversely affecting the stable unsaturated compounds therein.

Another object of the invention is to provide a process for improving hydrocarbon oils by removing color bodies therefrom.

Another object of the invention is to provide a simple 7 3 process for removing metallic constituents from the hydrocarbon oils.

It is a further object of the present invention to provide a process ior refiuing catalytic reforming charging stock which is rapid-and efii'cieut and-whichrequires only small quantities ofireactants.

It is another object of the invention to provide aninexpensive, highly-efficient method for reducing the.content of metal compounds in napthas and. similar light petroleumfractions.

Inaccordance with the invention, Itreat the hydrocarbonoil stock with a small quantity of boron chloride, hereinafter referred to as boron chloride treating agent, to effect reaction between the boron chloride treating agent and the undesired constituents of the hydrocarbon, oil being treated. The boron chloride treating agent is used in an amount corresponding to at least 0.01% by Weight, preferably 0.10, to 2.5% by weight, of'the oil treated, and is intimately mixed with the hydrocarbon oil for a short period of. time, eg. one-half minute to thirty. minutes, and the oil is then separated from the boron chloride reaction products. The boron chloride treating agent and the associated v constituents of the oil stratify as a coalesced phase and the. refined hydrocarbon oil forms apurified phase. The coalesced phase is readily separated, by decantation, centrifuging or other convenient means, from the. purified phase and theboron chloride treating agent separated; from the coalesced phase. The refined oil which forms the purified phase. is then processed in the usual manner.

It i5 a fe ur f a nv nt o hat h t sa ms with he ro h p ds r at n agent r sul s n sti m al. he p e ent. n the h dr sa bqa li eat d of ph l ic. sen iments. p r ularl qll d ar ns a q tls q bsne aphal sn s r sin n e. i ul omp unds. par qularlyclic. sulfiur cpmnounds n i h. lec l r e t, ulf mpoun s. nitrogen m- Pounds... xysqaccmpqu ds 9 0f bodie un ab atur ted. mands. nd. me a ic onst ent -I t 1s aiurther feature oh my processthat the treatment ithth h n hl isle rcat n ag nt su s n h ssl ti e e sv Q nst b unsa at d mpo ds, mentioned, without adversely affecting or. removing the abl u sat ate cqmpqnnds.

It is a, further feature of my inventioulhatihetreatmcnt h bo n c1 1. idetr at n ent applicable to, and effeetiye, upon a wide variety of hydrocarbon oils su h s rude. l a ht ns sn n i r ckcd aso ofthermal and/or catalytic origin, kerosene, diesel oil, ubricat ng o tock h r na tack o Petr eum origin for catalytic crackers, coal-tar and coal tar distillates, liquid petroleum-likeproducts from the hydrogenationof solid fuels such as coal, shale oil and shale oil'distillatcs, oil from tar sands, other synthetic liquidfuel products, and the like. The foregoing list of products to whichthe invention is applicable isillustrative only and other hydrocarbon oil materials may beefiectively, treated in accordancewith my invention.

For example, treatment with boron chloride. treating agent in accordance with my invention is particularly suitable for the reclaiming of used.- lubricating oil,- e.g., dirty lubricating oils removed from thecrankcases of motor vehicles. In accordance with my process, the used lubricating oil may-be restoredto substantiallyits originalstate. Furthermore, since it is a geueraltendency for these undesirable constituents to concentrate in the higher molecular weight portion of the oil, their removal by means of a boron chloride treating agent tends to lowerthe specific gravity of the oil. Some of these high molecular weight constituents removed are coloring bodies. Thus by this treatment the-color of the treated. hydrocarbon stock is generally improved. In heavy oils, such as lubricating oil stock, a distinct bloom is produced.

. Que. particularly. useful. application. of; my. process is 4 the removal of entrained undesirable constituents from vacuum gas oil. The action of the boron chloride treating agent in accordance with the invention is not limited, however, in its utility to the removal of the above-mentioned undesired constituents but is efiective, for example, in separating light aromatic compounds from paraffins and naphthenes and in the improvement of the viscosity index and viscosity gravity content of a lubricating oil stock byincreasing. its paraifinicity. Thismethod-is also effective in separating asphaltic materials from waxes of the samemolecular. weight. range. Thus, in the case of crude oils which contain both waxes and asphalts, which cannot be separated by vacuum distillation, this method is particularly eifectivein producing a good grade asphalt.

After the removal of the coalesced phase from the reaction mixture, not only may the coalesced phase be used for recovery of the boron chloride treating agent employedbut it may be usedas a source oicommercially valuable forms of the extracted impurities. For example, thesulfur, removed from high-sulfur crude oils by treatment of the oils in accordance with. my invention is concentrated. in a relativelyv small fraction after treatmentand the recovery of elemental sulfur is easily effected. My invention, therefore, provides a means for economically recovering. elementary sulfur from hydrocarbon oils.

Other objects and features of my invention will be readily apparent to those skilled in the art from the fol: lowing detailed description of my hydrocarbon oil treating process. I

The theoretical background of the invention involves the property of boron chloride to form many coordination compounds or adducts, as they are sometimes called. Actually the. number of such coordination com-. pounds is very great, whereas the number. of different atoms whichhave been found todonate electron pairs to the boron atom is rather small. Within thisexclusive group, however, are nitrogen, oxygen, sulfur and carbon. Boron chloride is a very efficient catalyst in many reactions.

The prevailing theory is. that the catalytic activity of boron chloride is based onthe. electrophilic character oi the boron chloride molecule. Asa consequence of its behavior as an acid? it is assumed to react with an organic moleculewhich acts as a base to produce a co ordination compound. The molecular boron chloride is then. assumed toion-ize in such manner that theacidity of the medium is increased.

In accordance with the invention, as soon as the sul-, fur, nitrogen and oxygen-containing compoundshave had an opportunity to react with the boron chloride, a series of. coordination compounds is, formed and separates out from thepurified oil as a coalesced phase, either in solid form or semi-solid form in admixture with or-in solutionin theadded agent. The reaction is almost instantaneous when intimate contact is provided.

Inasmuch as the amount of undesirable compoundsin the oil treated is relatively small, as a rule totaling not; more than 10%, excluding asphalt, it follows that the amount 0E boron chloride treating agent required can be small. Aspreviously mentioned, at least 0.01%; by weight, preferably 0.10 to 2.5% by Weight of the treating agent is used; It will be understood that the quantity of boron chloride treating agent used will varyfrom oil' to oil depending upon the nature of the mate rials'tobe. removed. For example, when the process of the invention'is'used for separating aromatic hydro: carbons from. mixtures containing the aromatic hydro; carbons in admixture with non-aromatic hydrocarbons, e.g. paraffinsand naphthenes, a large excess of the boron, halidecompound is advantageously used. 7

The temperature at which I carry out my process is in most instances room temperature or slightly below,

' e,g. 10 (3. However, when relatively viscous oilsarev state, e.g. by heating them up to about 60 C. In general, therefore, my process is carried out at temperatures of about C. to 60 C. Alternatively or concurrently, I may dilute the viscous oil with an inert solvent such as a parafiinic or naphthenic hydrocarbon or hydrocarbon fraction, e.g. n-heptane, n-hexane, cyclohexane, methyl cyclohexane, and the like.

The contact between the boron chloride treating agent and the oil needs only to be sufiicient to permit the compound to react to effect separation of the undesired constituents from the oil. Generally speaking, the contact time is between one-half minute and thirty minutes, although longer contact times may be utilized without departing from the scope of the invention.

[While I do not mean to be bound by any particular theory with respect to the reactions involved between the oil treated and the boron chloride treating agent in accordance with my process, the surprising action of these compounds in removing asphaltic substances is apparently due to the fact that the asphaltic substances in crude oils may be considered as forming with the oils a colloidal system with resinous materials serving as protective colloids. The boron chloride reacts with the resins to form coordination compounds and thus removes the protective colloid from the system thereby forcing the asphaltenes and like asphaltic constituents to coalesce and pass into the coalesced phase.

' Similarly, in the case of sulfur removal in accordance with my invention, I believe that the boron chloride forms coordination compounds with the sulfur bodies in the oil treated and thus the rwction may be considered as a pseudo-chemical reaction as distinct from the purely physical action of commercial sulfur, e.g. mercaptan, removal processes or the chemical action of catalytic hydrodesulfurization. The boron chloride makes no distinction among mercaptans, sulfides and cyclic sulfur compounds, such as thiophene, and the relative quantities of each removed are governed solely by mass action law.

It is known that boron chloride is a powerful polymerization catalyst. However, in accordance with my invention wherein my refining treatment is carried out at low temperature, e.g. room temperature and at normal atmospheric pressure, the polymerization of the desirable mono-olefins is avoided while polymerization of the undesired diolefins and acetylenes is promoted.

I have also found that boron chloride exhibits a preferenial afiinity for aromatic compounds over parafiinic and naphthenic compounds. Thus, my process provides a new method ofseparating aromatic compounds from parafiinic and naphthenic compounds. When applied to lubricating oil stocks, my process serves to increase the paraflinity of the stock by selectively extracting the more aromatic constituents. As previously mentioned, the coalesced phase containingthe impurities may be separated from the purified phase by any convenient means, e.g. decantation, centrifuging and the like. Similarly, known methods of liquidliquid extraction either batch-operated or continuous, such as the well known Podbielniak centrifugal contactor, may be used.

Boron chloride can be recovered by distillation. For instance, B01 boils at 125 C. which can easily be stripped off from the extract. But, inasmuch as the quantities of reagent used are exceedingly small and BCI;, is inherently a very inexpensive chemical, its recovery, in most instances is not necessary.

The following examples will serve to illustrate more fully the operation and advantages of the present invention:

' Example I To three samples each comprising 100 parts by weight of 380 API Saudi Arabia crude oil were added, respec tively, 0.075, 0.15 and 0.25 part by Weight of boron 6 chloride at room temperature. Each sample was shaken vigorously for five minutes. After settling, the upper layer was decanted. The specific gravity, Conradson carbon, residue and sulfur content of the upper layer which comprises the refined oil, were then determined, and of a sample of the crude oil treated, with the follow ing results:

p The lower layer in each case was semi-solid and asphaltic in character.

The lower strata (the coalesced strata) from the three samples were combined and were found to be soft asphalt with a softening point of F.-

Example II A 314 API Kuwait crude oil was treated with 0.1 percent by weight B01 at room temperature. The improvement in properties is set forth below:

Original Treated Oil 011 Volume Percent Yield 91 API a1. 4 32.1 Conradson Carbon Residue, W. Percent 5 3. 50 Sulfur, Wt. percent 2. 65 2. 25 Nickel,'p.p.m 8 4 Vanadium, p.p.m 22 11 Example 11! A vacuum gas oil fraction from Kuwait crude oil was treated with 0. 05% by weight BCl at 70 F. The improvement in properties are shown below:

Original Treated Oil 011 Volume Percent Yield 100 98 Sulfur, Wt. percent 3. 49 1. 62 Nitrogen, Wt. percent 0.0221 0.012 APT l7. 6 20 Carbon Residue, Wt. percent 1.945 1.37 Color ASTM 8 3 Example I V ,A heavy catalytic cracked naphtha was treated with 0.2 percent of BCl The treated naphtha was separated from the sludge formed, washed with water, and The improvement in properties will be seen from the following:

B 01, Original treated and rerun Volume yield, percent" 100 95 Sulfur, Wt. percent 0.35 0. 33 Copper dish gum, mg./100 ml 50 It will be obvious to those skilledin the art that various changes and modifications may be made in the process hereinabove described without departing from the scope of the invention as defined in the appended claims and it is intended, therefore, that all matter contained the qresoin r e cr pti n hal n emr t d a llusr tiye onl nd no n; a t-if some T What t a m nd esireto se u x Le ter at gt s i A P es e eat nsr si orea q lqtarnms deleter ous mli ll icsto remqve a dteriousm es-" ere ro h ch p ises. nt ma lymb na e hydrocarbon oil at substantially atmospheric pressure with a treating agent consisting essentially of boron chloride, said treatingagent being'employed in, a quantity of at least about-0.01% by weight, causing the intimately oilitotseparate into a reactant phase containing-the ma or proportion of the treating agent and the impurities separated thereby andta purified phase, and separatingsaid purified phase from said reactant phase,

2. A process of treating a hydrocarbon oil containing deleterious impurities torernove-said deleterious impurities therefrom which comprises, intimately mixing said hydrocarbon oil at substantially atmospheric pressure for /2 minute to 30 minutes with a treating agent consisting essentially of boron chloride, said treating agent being uirloyedflin aquant ty f at astab91 .tQ-,Q b w xbti causing the intimately mixed oil to separate into areactant' phase containing the major proportion ofthetreating agent and the impurities separated thereby and a purifiedphase, and separating saidpurified phasefi'om said reactant phase. 7

3. A process of treating a hydrocarbon oil'containing deleterious impurities to, remove, said deleterious impurities therefrom which comprises, intimately. mixing said hydrocarbon l at ant al y osphe c p ss e with a treatingagent consisting essentially, of boron chloride, said treating agent being employed in a quantity of about 0.1% to 2.5% by weight, causing the intimately mixed oil to separate into a reactant phase containing the major proportion of the treating agent and the impurities separated thereby and a purified'phase, and separating said purified phase from said reactant phase,

4. A process of treating athydrocarbon oil containing deleterious impurities to remove said'deleterious impurities therefrom which comprises, intimately mixing said hydrocarbon oil at substantially atmospheric pressure at a temperature between about 1.0" C. and 60 C. with a treating agent consisting essentially of boron chloride, said treating agent being employed in aquantity of at least about- 0.01% byweight, causing theintimately mixed oil to separate into a reactant phase containing-the major proportion of the treating agent and the impurities separated thereby and a purified phase, and separating said purified phase from said reactant phase.

5. A process of treating a hydrocarbon oil containing deleterious impurities to remove said" deleterious impurities therefrom which comprises, intimately mixing said hydrocarbon oil at substantially atmospheric pressure at a temperature between about 10 C. and-60 C. for V2 minute to 30 minutes with a treating agent consisting essentially of boron chloride, said treating agent being employed in a quantity of about 0.1% to 2.5% by weight, causing the intimately mixed oil to separate into a reactant phase containing the major proportion of the treating agent and the impurities separated thereby and a purifiedphase, and-separating said purified phase from said reactant phase.

6. A process of treating a hydrocarbon oil containing deleterious impurities selected from the group consisting of asphaltic bodies, sulfur bodies, resins, nitrogen compounds, oxygen compounds, color bodies, unstable unsaturated compounds, and metallic constituents, to remove said impurities. therefrom which comprises, intimately mixing said hydrocarbon oil at substantially atmospheric pressure with a treating agcutconsistingessens tially of boronichloride, said treating agent being emplpyed-in, a quantity of at least about 0.01 %l by, weight, causing the, intimately mixed oil to sep fllla q into. a re astant-hhasecqma nins emai p onq s o he r ius aseut n e rn ss spar edathsr y a d a purified phase, and separating said purified phase horn said reactant phase,

. 7. A processof treating a hydrocarbon oilcontaining deleterious impurities selected from the group consisting of asphaltic bodies, sulfur bodies, resins, nitrogen compounds, oxygen compounds, color bodies, unstablcruur saturated compounds, and metallic constituents, to, remove said impurities therefrom which comprises, intimately mixing 'said hydrocarbon oilat substantially at: mospheric pressure for /2 minute to 30 minutes with, a treating agent consisting essentially of boron chloride, said treating agent being employed, in a quantity of at; least about 0.01 by weight, causing the intimately mixed oil to separate into a reactantphasecontainingthemajor proportion of thetreating agent and the impuritiesseparated thereby and a purified phase, and separating said purified phase from said reactant phase. a

8, A process of treating a hydrocarbon oil containingdeleterious impurities selected from the, group consisting of asphaltic bodies, sulfur'bodies, resins, nitrogen com: pounds, oxygen compounds, color bodies, unstable unr. satura d mp d d m l c. uen t emove said impurities therefrom which comprises, intia mately mixing said hydrocarbon oil at substantially at-. mospheric pressure with a treating agent consisting essen. tially of boron chloride, said treating agent being employed' in a quantity of about 0.1% to 2.5%, by weight,

causing the intimately mixed oil to separate into a re actant phase containing the major proportion of the treat: ing agentand the impurities separated thereby and a purifled phase, and separating said purified'phase from saidreactant phase,

9. A process of treating a hydrocarbonoil containing deleterious impurities selected from the group'consisting of asphaltic bodies, sulfur bodies, resins, nitrogen compounds, oxygen compounds, color bodies, unstable. unsaturated compounds, and metallic constituents, to rc-v move said impurities therefrom which comprises, intimately mixing said hydrocarbon oil at substantially. ate mospheric pressure at a temperature between about 10 C and 60 C. with a, treating agent consisting-essential.- ly of boron chloride, said treating agent being employed ina quantity of at least about 0.01% by weight, causing the intimately mixed oil to separate into a reactant, phase containing the major proportion of' the treating; agent and the impurities separated thereby and a purified phase, and separating saidpurified phase from; said, reactant phase.

10. A process of treating a hydrocarbon oil contain-, ing deleterious impurities selected from the group, con: sisting; of asphaltic bodies, sulfur bodies, resins, nitrogen compounds, oxygen compounds, color bodies,l unstable unsaturated compounds, and metallic constit uents, to remove said impurities therefrom which com prises, intimately mixing said hydrocarbon oil; at substantially atmospheric pressure ata temperature, between about 10 C. and 60 C. for /2 minute; to 30- minutes with a treating agent consisting essentially of boron chloride, said treating agent being employed inia quantity of about 0.1% to 2.5% by weight, causing the intimately mixed oil to separate into a reactant phase containing the majorproportion of the treating agent and the'impurities separated thereby and a purified phase, and separating said purifiedphase from said reactant phase.

ll. A process of treating alight hydrocarbon oil of the type used as feed-for catalytic reforming operations and containing metallic compounds having a poisoning action upon catalysts used in catalytic reforming which comprises, intimately mixing saidhydrocarbonoil at substantially atmospheric pressure with a treating agent consisting essentially of boron chloride, said treating agent being employed in a quantity; of at least about 0.01% y ht, c u i g n imately mix d 01 o separate into a reactant phase containing the major-1 9:

portion of the treating agent and the impurities separated thereby and a purified phase, and separating said purified phase from said reactant phase.

12. A process of treating a light hydrocarbon oil of the type used as feed for catalytic reforming operations and containing metallic compounds having a poisoning action upon catalysts used in catalytic reforming which comprises, intimately mixing said hydrocarbon oil at substantially atmospheric pressure for /2 minute to 30 minutes with a treating agent consisting essentially of boron chloride, said treating agent being employed in a quantity of at least about 0.01% by weight, causing the intimately mixed oil to separate into a reactant phase containing the major proportion of the treating agent and the impurities separated thereby and a purified phase, and separating said purified phase from said reactant phase.

13. A process of treating a light hydrocarbon oil of the type used as feed for catalytic reforming operations and containing metallic compounds having a poisoning action upon catalysts used in catalytic reforming which comprises, intimately mixing said hydrocarbon oil at substantially atmospheric pressure with a treating agent consisting essentially of boron chloride, said treating agent being employed in a quantity of about 0.1% to 2.5% by weight, causing the intimately mixed oil to separate into a reactant phase containing the major proportion of the treating agent and the impurities separated thereby and a purified phase, and separating said purified phase from said reactant phase.

14. A process of treating a light hydrocarbon oil of the type used as feed for catalytic reforming operations and containing metallic compounds having a poisoning action upon catalysts used in catalytic reforming which comprises, intimately mixing said hydrocarbon oil at substantially atmospheric pressure at a temperature between about C. and 60 C. with a treating agent consisting essentially of boron chloride, said treating agent being employed in a quantity of at least about 0.01% by weight, causing the intimately mixed oil to separate into a reactant phase containing the major proportion of the treating agent and the impurities separated thereby and a purified phase, and separating said purified phase from said reactant phase.

15. A process of treating a light hydrocarbon oil of the type used as feed for catalytic reforming operations and containing metallic compounds having a poisoning action upon catalysts used in catalytic reforming which comprises, intimately mixing said hydrocarbon oil at substantially atmospheric pressure at a temperautre between about 10 C. and 60 for /2 minute to 30 minutes with a treating agent consisting essentially of boron chloride, said treating agent being employed in a quantity of about 0.1% to 2.5% by weight, causing the intimately mixed oil to separate into a reactant phase containing the major proportion of the treating agent and the impurities separated thereby and a purified phase, and separating said purified phase from said reactant phase.

16. A process of treating crude oil, residue and like heavy hydrocarbon oil characterized by a significant content of sulfur compounds to reduce the quantity of said sulfur compounds in said oil which comprises, intimately mixing said hydrocarbon oil at substantially atmospheric pressure with a treating agent consisting essentially of boron chloride, said treating agent being employed in a quantity of at least about 0.01% by weight, causing the intimately mixed oil to separate into a reactant phase containing the major proportion of the treating agent and the sulfur compounds separated thereby and a purified phase, and separating said purified phase from said reactant phase.

17. A process of treating crude oil, residue and like heavy hydrocarbon oil characterized by a significant content of sulfur compounds to reduce the quantity of said sulfur compounds in said oil which comprises, intimately mixing said hydrocarbon oil at substantially atmospheric pressure for /2 minute to 30 minutes with a treating agent consisting essentially of boron chloride, said treating agent being employed in a quantity of at least about 0.01% by weight, causing the intimately mixed oil to separate into a reactant phase containing the major proportion of the treating agent and the sulfur compounds separated thereby and a purified phase, and separating said purified phase from said reactant phase.

18. A process of treating crude oil, residue and like heavy hydrocarbon oil characterized by a significant content of sulfur compounds to reduce the quantity of said sulfur compounds in said oil which comprises, intimately mixing said hydrocarbon oil at substantially atmospheric pressure with a treating agent consisting essentially of boron chloride, said treating agent being employed in a quantity of about 0.1% to 2.5 by weight, causing the intimately mixed oil to separate into a reactant phase containing the major proportion of the treating agent and the sulfur compounds separated thereby and a purified phase, and separating said purified phase from said reactant phase.

19. A process of treating crude oil, residue and like heavy hydrocarbon oil characterized by a significant content of sulfur compounds to reduce the quantity of said sulfur compounds in said oil which comprises, intimately mixing said hydrocarbon oil at substantially atmospheric pressure at a temperature between about 10 C. and 60 C. with a treating agent consisting essentially of boron chloride, said treating agent being employed in a quantity of at least about 0.01% by weight, causing the intimately mixed oil to separate into a reactant phase containing the major proportion of the treating agent and the sulfur compounds separated thereby and a purified phase, and separating said purified phase from said reactant phase.

20. A process of treating crude oil, residue and like heavy hydrocarbon oil characterized by a significant content of sulfur compounds to reduce the quantity of said sulfur compounds in said oil which comprises, intimately mixing said hydrocarbon oil at substantially atmospheric pressure at a temperature between about 10 C. and 60 C. for /2 minute to 30 minutes with a treating agent consisting essentially of boron chloride, said treating agent being employed in a quantity of about 0.1% to 2.5 by weight, causing the intimately mixed oil to separate into a reactant phase containing the major proportion of the treating agent and the sulfur compounds separated thereby and a purified phase, and separating said purified phase from said reactant phase.

References Cited in the file of this patent UNITED STATES PATENTS 2,767,120 Stuart Oct. 16, 1956 

1. A PROCESS OF TREATING A HYDROCARBON OIL CONTAINING DELETERIOUS IMPURITIES TO REMOVE SAID DELETERIOUS IMPURITIES THEREFROM WHICH COMPRISES, INTIMATELY MIXING SAID HYDROCARBON OIL AT SUBSTANTIALLY ATMOSPHERIC PRESSURE WITH A TREATING AGENT CONSISTING ESSENTIALLY OF BORON CHLORIDE, SAID TREATING AGENT BEING EMPLOYED IN A QUANTITY OF AT LEAST ABOUT 0.01% BY WEIGHT, CAUSING THE IMTIMATELY MIXED OIL TO SEPARATE INTO A REACTANT PHASE CONTAINING THE MAJOR PROPORTION OF THE TREATING AGENT AND THE IMPURITIES SEPARATED THEREBY AND A PURIFIED PHASE, AND SEPARATING SAID PURIFIED PHASE FROM SAID REACTANT PHASE. 